ES2253262T3 - POLYMERIZATION PROCEDURE - Google Patents

Abstract

The present invention relates to a process for polymerizing olefin(s) in the presence of metallocene-type catalyst compound, an activator and an inorganic oxide support, a Group 13 containing compound and a carboxylic acid, where the carboxylic acid is added to the polymerization reactor separately. The invention also relates to a process for transitioning from one polymerization catalyst to another.

Description

Polymerization procedure

Field of the invention

The present invention relates to a process for polymerizing olefin (s) using a compound metallocene catalyst comprising a Group 4 metal, a inorganic oxide support, a carboxylic acid and a compound containing Group 13 metal.

Background of the invention

Advances in polymerization and catalysis have resulted in the ability to produce many new polymers that have useful improved physical and chemical properties in a wide variety of superior products and applications. With the development of new catalysts, has expanded greatly the choice of the type of polymerization (solution phase, suspension, high pressure or gas) to produce a polymer particular. Also, advances in the technology of the polymerization have provided more effective procedures, highly productive and economically improved. Especially illustrative of these advances is the development of technology that uses metallocene ligand type catalyst systems bulky. In particular, in a phased procedure in suspension or gas where a catalyst system is typically used  supported, there are several different methods described in the art to support metallocene ligand type catalyst systems bulky. Regardless of these technological advances in the polyolefin industry, there are still common problems, as well as new challenges associated with the operability of the process. For example, the trend for a procedure in gas phase or suspended phase to get dirty or form sheets It remains a challenge.

The evidence of, and the solutions for, the various procedural operability problems have been addressed by many in the art. For example, the patents of United States numbers 4,792,592, 4,803,251, 4,855,370 and 5,319,657 all discuss techniques to reduce static generation in a polymerization process by introducing, for example, water, inorganic chemical alcohols, ketones and / or additives; the PCT publication WO 97/14721, published April 24, 1997, discusses the suppression of fines that can cause the formation of sheets adding an inert hydrocarbon to the reactor; the patent of United States No. 5,627,243 discusses a new type of plaque distributor for use in reactors in gas phase bed fluidized; PCT publication WO 96/08520 discusses avoiding introduction of a scrubber into the reactor; the states patent United No. 5,461,123 discusses using sound waves to reduce sheet formation; U.S. Patent No. 5,066,736 and EP-A1 0 549 252 discuss the introduction of a reactor activity retarder to reduce agglomerates; U.S. Patent No. 5,610,244 refers to feed replacement monomer directly in the reactor above the bed to prevent fouling and improve the quality of the polymer; U.S. Patent No. 5,126,414 discusses including an oligomer removal system to reduce fouling of the distribution plate and provide gel free polymers; EP-A1 0 453 116, published on October 23, 1991, discusses the introduction of antistatic agents in the reactor to reduce the amount of sheets and agglomerates; U.S. Patent No. 4,012,574 discusses adding a surfactant compound, a group perfluorocarbon, to the reactor to reduce fouling; the U.S. Patent No. 5,026,795 discusses the addition of a antistatic agent with a liquid vehicle to the area of polymerization in the reactor; U.S. Patent No. 5.410.002 discusses using a supported catalyst system of conventional Ziegler-Natta titanium / magnesium where a selection of antistatic agents is added directly to the reactor to reduce fouling; State patents No. 5,034,480 and 5,034,481 discuss a reaction product of a titanium catalyst from Ziegler-Natta conventional with an antistatic to produce ethylene polymers ultra high molecular weight; U.S. Patent No. 3,082,198 discusses introducing an amount of a carboxylic acid which depends on the amount of water in a procedure to polymerize ethylene using an organometallic catalyst of titanium / aluminum in a hydrocarbon liquid medium; and the patent of the United States No. 3,919,185 describes a procedure in suspension using a non-polar hydrocarbon diluent using a Ziegler-Natta or Phillips type catalyst  conventional and a polyvalent metal salt of an organic acid having a molecular weight of at least 300.

There are several other known methods to improve operability that include coating polymerization equipment, for example, treating the walls of a reactor using compounds of chrome, as described in United States patents numbers 4,532,311 and 4,876,320; inject several agents into the process, by example, PCT publication WO 97/46599, published on 11 December 1997, discusses feeding in an inclined area in a polymerization reactor a catalyst system of type metallocene, soluble and unsupported, and injecting agents anti-fouling or antistatic in the reactor; control the polymerization rate, particularly at startup; Y reconfigure the reactor design.

Others in the art to improve operability of the procedure have discussed modifying the catalyst system preparing the catalyst system in different ways. For example, the methods in the art include combining the components of the catalyst system in a particular order; manipulate the relationship of the various components of the catalyst system; vary the time of contact and / or temperature when the components are combined of a catalyst system; or simply add various compounds to the catalyst system. These techniques or their combinations are discussed in the bibliography. They are especially illustrative in the technical procedures and methods of preparation to produce voluminous ligand metallocene type catalyst systems, more particularly metallocene catalyst systems of bulky ligand supported with reduced trends to fouling and better operability. Examples of these include: WO 96/11961, published on April 26, 1996, discusses as a component of a supported catalyst system an agent antistatic to reduce fouling and sheet formation in a gas, suspension or bath polymerization process liquid; U.S. Patent No. 5,283,278 is directed toward prepolymerization of a metallocene catalyst or a conventional Ziegler-Natta catalyst in presence of an antistatic agent; United States patents Nos. 5,332,706 and 5,473,028 have resorted to a particular technique to form a catalyst by incipient impregnation; the U.S. Patent Nos. 5,427,991 and 5,643,847 describe the chemical binding of non-coordinating anionic activators to brackets; U.S. Patent No. 5,492,975 discusses polymer-bound metallocene type catalyst systems; the U.S. Patent No. 5,661,095 discusses enduring a metallocene catalyst on a copolymer of an olefin and an unsaturated silane; PCT publication WO 97/06186, published on February 20, 1997, teaches to separate inorganic impurities and organic after the formation of the type catalyst itself metallocene; PCT publication WO 97/15602, published on 1 May 1997, discusses easily supported metal complexes; the PCT publication WO 97/27224, published July 31, 1997, refers to forming a supported transition metal compound in the presence of an unsaturated organic compound that has at least a double terminal link; and the document EP-A2-811 638 discusses using a metallocene catalyst and an activating cocatalyst in a polymerization process in the presence of an agent antistatic containing nitrogen. The document AP-A-0 803 514 suggests catalysts of supported metallocene and the use of metal salts of acids carboxylics to reduce coatings in polymerizations of olefins.

Although all these possible solutions can somewhat reduce the level of fouling or sheet formation, some are expensive to use and / or may not reduce fouling and sheet formation to a level sufficient to operate with success a continuous procedure, particularly a procedure Commercial or large scale.

Therefore, it would be advantageous to have a improved polymerization process that would result in the  increased reactor operability.

Summary of the invention

This invention creates a procedure for polymerize olefin (s) in a polymerization reactor in presence of a metallocene catalyst compound comprising a Group 4 metal, an inorganic oxide support, an acid carboxylic and a compound containing Group 13 metal; at that the catalyst compound is supported on an oxide inorganic to form a metallocene catalyst system supported, and in which the metallocene catalyst system supported is added to the reactor separately from the compound that contains Group 13 metal and carboxylic acid; and in which the mole ratio of carboxylic acid to compound containing Group 13 metal is from 0.5 to less than 2.0.

The invention is also directed to a process to polymerize olefin (s) in a reactor in the presence of a catalyst system, the catalyst system comprising a metallocene catalyst compound comprising a metal of Group 4, a support and an activator, comprising the procedure the stages of:

(to)

    introduce a compound containing Group 13 metal into the reactor; followed by

(b)

    introducing a carboxylic acid and the catalyst system into the reactor, the carboxylic acid added separately from the system catalyst; and wherein the mole ratio of carboxylic acid to Group 13 metal containing compound is from 0.5 to lower that 2.0.

In another embodiment, the invention is directed to a process to polymerize one or more olefin (s) in a reactor in the presence of a metallocene catalyst compound that it comprises a Group 4 metal, an inorganic oxide support and a compound containing Group 1 metal, in which an acid carboxylic is added to the reactor in an amount sufficient to substantially maintain the catalyst activity of polymerization; in which the catalyst compound is supported over inorganic oxide to form a catalyst system of supported metallocene, and in which the catalyst system of Supported metallocene is added to the reactor separately from the compound containing Group 13 metal and carboxylic acid; Y wherein the mole ratio of carboxylic acid to compound that Contains Group 13 metal is from 0.5 to less than 2.0.

Detailed description of the invention Introduction

The invention is directed to a process for polymerizing olefin (s) in a reactor in the presence of a catalyst system and a carboxylic acid. It was surprisingly discovered that introducing a carboxylic acid into a polymerization process in which a Group 13 metal-containing compound is present, either with the catalyst system or separately introduced into the reactor, results in a process that has improved operability. Although it is not desired to be bound by any particular theory, it is believed that the carboxylic acid and the metal-containing compound of Group 13, which could be components of the catalyst system, react to form a metal carboxylate salt or some other compound in situ in the polymerization process that is benign for the process. For example, in U.S. Patent Application Serial No. 09 / 397,409, filed September 16, 1999, and U.S. Patent Application Serial No. 09 / 397,410, filed September 16, 1999, it discovered that using a metal carboxylate salt together with a bulky ligand metallocene catalyst system or a transitional Ziegler-Natta catalyst system, preferably, a supported bulky ligand metallocene catalyst system, substantially improves the operability of the process .

Transition metal catalysts of conventional type

Type transition metal catalysts Conventional are the Ziegler-Natta catalysts traditional and very chrome type Phillips catalysts known in the art. Examples of metal catalysts from Conventional type transition are discussed in the patents of United States numbers 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,789,359 and 4,960,741, all of which are incorporated completely here for reference. The catalyst compounds of transition metal of conventional type that can be used in the present invention include transition metal compounds of the Groups III to VIII, preferably IVB to VIB of the Periodic Table of the Elements.

These conventional type transition metal catalysts can be represented by the formula: MR x, where M is a metal of Groups IIIB to VIII, preferably Group IVB, more preferably titanium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M. Non-limiting examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examples of conventional transition metal catalysts where M is titanium include TiCl 4, TiBr 4, Ti (OC 2 H 5) 3 Cl, Ti (OC 2) H 5) Cl 3, Ti (OC 4 H 9) 3 Cl, Ti (OC 3 H 7) 2 Cl 2, Ti (OC_ {2 H5) 2
Br 2, TiCl 3. 1/3 AlCl 3 and Ti (OC 12 H 25) Cl 3.

Conventional transition metal catalyst compounds based on magnesium / titanium electron donor complexes that are useful in the invention are described in, for example, U.S. Patent Nos. 4,302,565 and 4,302,566, which are incorporated completely here for reference. The derivative MgTiCl 6 (ethyl acetate) 4 is particularly preferred. British Patent Application 2,105,355, incorporated herein by reference, describes several conventional vanadium catalyst compounds. Non-limiting examples of conventional vanadium catalyst compounds include trihalide, alkoxyhalides and vanadyl alkoxides such as VOCl 3, VOCl 2 (OBu), where Bu is butyl, and VO (OC 2 H 5) )_{3}; vanadium tetrahalide and vanadium alkoxyhalides such as VCl 4, VCl 3 (OBu); vanadium and vanadyl acetylacetonates and chloroacetylacetonates, such as V (AcAc) 3
and VOCl 2 (AcAc), where (AcAc) is acetylacetonate. The preferred conventional type vanadium catalyst compounds are VOCl3, VCl4 and VOCl2 -OR, where R is a hydrocarbon radical, preferably a C 1 to C 10 aliphatic or aromatic hydrocarbon radical }, such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

The type chrome catalyst compounds conventional, often referred to as type catalysts Phillips, suitable for use in the present invention include CrO 3, chromocene, silyl chromate, chromyl chloride (CrO 2 Cl 2), chromium 2-ethylhexanoate, chromium acetylacetonate (Cr (AcAc) 3) and the Similar. Non-limiting examples are described in the patents. of the United States numbers 2,285,721, 3,242,099 and 3,231,550, which fully incorporated here by reference.

Still other catalyst compounds and systems transition metal catalysts of conventional type suitable for use in the present invention are described in the U.S. Patents Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 and published documents EP-A2 0 416 815 and EP-A1 0 420 436, all of which incorporate here by reference. The metal catalysts of conventional type transition of the invention may have also the general formula M '1 M''X_ {2t} Y_ {u} E, where M' is Mg, Mn and / or Ca; t is a number from 0.5 to 2; M '' is a metal of Ti, V and / or Zr transition; X is a halogen, preferably Cl, Br or I; And it can be the same or different and is halogen, alone or in combination with oxygen, -NR2, -OR, -SR, -COOR, or -OSOOR, where R is a hydrocarbyl radical, in particular an alkyl radical, aryl, cycloalkyl or arylalkyl, acetylacetonate anion in a quantity that satisfies the valence state of M '; u is a number from 0.5 to 20; E is an electron donor compound selected from the following classes of compounds: (a) esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d) amines; (e) esters of carbonic acid; (f) nitriles; (g) phosphoramides; (h) phosphoric and phosphorous acid ethers, and (j) phosphorus oxychloride. Other catalysts may include cationic catalysts such as AlCl 3 and other catalysts  of cobalt and iron well known in the art.

Typically, these catalyst compounds of transition metal of conventional type, excluding some Chromium catalyst compounds of conventional type are activated with one or more of the conventional type cocatalysts described then.

Conventional type cocatalysts

Cocatalyst type compounds conventional for the above metal catalyst compounds Conventional type transition can be represented by the formula M 3 M 4 x X 2 c c R 3 b-c, in which M3 is a metal of Group IA, IIA, IIB and IIIA of the Periodic table of elements; M4 is a metal of Group IA from the Periodic Table of the Elements; v is a number from 0 to one; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and in which b minus c is at least 1. Other organometallic cocatalyst compounds of conventional type for the previous metal catalysts of conventional type transition have the formula M 3 R 3 k, where M 3 is a metal of Group IA, IIA, IIB or IIIA such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium; k is equal to 1, 2 or 3, depending on the valence of M3 which valence, in turn, depends on the Group particular to which M3 belongs; and each R3 can be any monovalent hydrocarbon radical.

Non-limiting examples of compounds Group IA organometallic cocatalysts of the conventional type, IIA and IIIA useful with catalyst type compounds Conventional described above include methyl lithium, butyl lithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotasium, diethylcinc, tri-n-butylaluminum, diisobutyl-ethylboro, di-n-butylcinc and tri-n-amilboro and, in particular, aluminum alkyls such as trihexylaluminum, triethylaluminum, trimethylaluminum and triisobutylaluminum. Others Conventional type cocatalyst compounds include monoorganohalides and hydrides of Group IIA metals, and mono or diorganohalides and metal hydrides of Group IIIA. Examples no Limitations of such conventional type cocatalyst compounds include diisobutyl aluminum bromide, dichloride of isobutylboro, methylmagnesium chloride, ethylberyl chloride, ethyl calcium bromide, diisobutylaluminium hydride, hydride methylcadmium, diethylboro hydride, hexylberyl hydride, Dipropylboro Hydride, Octylmagnesium Hydride, Hydride butylcinc, dichloroboro hydride, dibromoaluminium hydride e bromocadmium hydride. Cocatalyst compounds organometallic conventional type are known for technical experts and a more complete discussion of these Compounds can be found in United States patents Nos. 3,221,002 and 5,093,415, which are fully incorporated here by reference

For the purposes of this specification of patent and of the appended claims, the compounds Transition metal catalysts of conventional type exclude those metallocene catalyst compounds discussed at continuation.

Metallocene catalyst compounds

Generally, the catalyst compounds of Metallocene type include semi and complete sandwich compounds that they have one or more bulky ligands attached to at least one atom of metal. Typical metallocene compounds are described. generally as containing one or more ligand (s) bulky (s) and one or more labile group (s) attached to at least one metal atom. In a preferred embodiment, at least one ligand is attached with η bond to the metal atom, most preferably with η 5 bond to the metal atom.

Ligands are generally represented by one or more ring (s) or open ring system (s), acyclic or fused or one of its combinations. These ligands, preferably the ring (s) or system (s) of rings, are typically composed of atoms selected from the Group 13 to 16 of the Periodic Table of the Elements, preferably, atoms are selected from the group consisting of carbon, nitrogen oxygen, silicon, sulfur, phosphorus, germanium, boron and aluminum, or one of its combinations. Most preferably, the (the) ring (s) or ring system (s) are make up (n) carbon atoms such as, but not limited to a, those cyclopentadienyl ligands or the structures of cyclopentadienyl type ligand or other ligand structure of similar performance such as a pentadiene ligand, one of cyclooctatetraendiyl or one of imide. The metal atom is preferably select from Groups 3 to 15 and from the series of lanthanides or actinides of the Periodic Table of the Elements. Preferably, the metal is a transition metal of Groups 4 to 12, more preferably Groups 4, 5 and 6, and most preferably The transition metal is from Group 4.

In one embodiment, the catalyst compounds Metallocene ligand type of the invention are represented by the formula:

(I) L A L B MQ_ n

where M is a metal atom of the Periodic Table of the Elements and can be a Group 3 metal to 12 or the lanthanide or actinide series of the Periodic Table of the Elements, preferably, M is a transition metal of the Groups 4, 5 or 6, more preferably M is a transition metal of the Group 4, even more preferably M is zirconium, hafnium or titanium. The ligands L A and L B are ring (s) or open ring system (s), acyclic or fused and are any auxiliary ligand system, including ligands of cyclopentadienyl or cyclopentadienyl type ligands not substituted or substituted and cyclopentadienyl type ligands substituted with heteroatoms and / or containing heteroatoms. Non-limiting examples of ligands include ligands of cyclopentadienyl, cyclopentaphenanthrenyl ligands, ligands of indenyl, bencindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, ligands Tile, pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125), pyrrolyl ligands, ligands of pirozolyl, carbazolyl ligands, borabencene ligands and similar, including their hydrogenated versions, for example, tetrahydroindenyl ligands. In one embodiment, L A and LB can be any other ligand structure capable of η to M bond, preferably η 3 to M bond and most preferably bond η 5. Still in another embodiment, the atomic molecular weight (M) of L A and L B exceeds 60 CU, preferably greater than 65 CU In another embodiment, LA and LB may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms to form a ring or system of  open, acyclic or preferably fused rings, by example, a heterocyclopentadienyl auxiliary ligand. Others bulky ligands L A and L B include, but are not limited to a, amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, corrines and others bulky polyazomacrocycles. Regardless, each LA and LB may be the same or different type of ligand that is attached to M. In one embodiment of formula (I), only one of either L A or L B is Present.

Regardless, each L A and L B can be unsubstituted or substituted with a combination of R groups substituents Non-limiting examples of substituent R groups include one or more of the selected group of hydrogen or radicals alkyl, alkenyl radicals or linear alkynyl radicals or branched, cycloalkyl radicals or aryl radicals, radicals acyl, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, radicals alkoxycarbonyl, aryloxycarbonyl radicals, carbomoyl radicals, alkyl or dialkylcarbamoyl radicals, acyloxy radicals, radicals acylamino, aroylamino radicals, linear alkylene radicals, branched or cyclic, or combinations thereof. In one embodiment preferred, substituent R groups have up to 50 atoms other than hydrogen, preferably from 1 to 30 carbons, which can also be substituted with halogens or heteroatoms or Similar. Non-limiting examples of R alkyl substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl groups, cyclopentyl, cyclohexyl, benzyl or phenyl, and the like, including all its isomers, for example, tertiary butyl, Isopropyl and the like. Other hydrocarbyl radicals include fluoromethyl, fluorethyl, difluorethyl, iodopropyl, bromohexyl, chlorobenzyl and organometaloid radicals substituted with hydrocarbyl, including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and organometaloid radicals halocarbyl substituted including tris (trifluoromethyl) silyl, methyl bis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and boron radicals disubstituted including dimethylboro, for example; and radicals of Group 15 element (pnictogen) substituted including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 element radicals (chalcogen), including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl sulfide. The R substituents other than hydrogen include atoms of carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like, including olefins such as, but not limited to, olefinically unsaturated substituents including vinyl terminated ligands, for example, but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two R groups adjacent, join to form a ring structure that has from 3 to 30 selected atoms of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron or one of its combinations Also, a substituent R group such as 1-butanyl can form a carbon sigma bond with the metal M.

Other ligands may be attached to the metal M, such as at least one labile Q group. For the purposes of this report Patent specification and the appended claims, the "labile group" expression is any ligand that can be extracted from a metallocene ligand type catalyst compound bulky to form a cation of the metallocene catalyst capable of polymerizing one or more olefin (s). In a embodiment, Q is a monoanionic labile ligand that has a bond Sigma to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2, so that the formula (I) above represents a neutral metallocene catalyst compound.

Non-limiting examples of ligand Q include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 atoms of carbon, hydrides or halogens and the like or one of their combinations In another embodiment, two or more Qs are part of a ring or fused ring system. Other examples of ligands Q include substituents for R as described above. and including cyclobutyl, cyclohexyl, heptyl, tolyl radicals, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis (N-methylanilide), dimethyl amide, dimethyl phosphide and the like.

In one embodiment, the catalyst compounds of the metallocene type of the invention include those of formula (I) where L A and L B are bridging each other by al minus a bridge group, A, so that the formula is represented by

(II) L A AL B MQ_ n

These bridge compounds represented by the formula (II) are known as catalyst type compounds metallocene with bridge. L A, L B, M, Q and n are as defined above. Non-limiting examples of bridge groups A include bridge groups containing at least one atom of Group 13 to 16, often referred to as a divalent residue such as, but not limited to at least one of a carbon, oxygen, nitrogen atom,  silicon, aluminum, boron, germanium and tin or one of its combinations Preferably, the bridge group A contains an atom of carbon, silicon or germanium, most preferably A contains the least one silicon atom or at least one carbon atom. The group bridge A may also contain substituent R groups as defined above, including halogens and iron. Examples no Limitations of bridge group A can be represented by R '2 C, R '2 Si, R' 2 SiR '2 Si, R' 3 Ge, R'P, where R 'is independently a radical group that is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, organometaloid substituted with hydrocarbyl, organometaloid halocarbyl substituted, disubstituted boron, Group element 15 substituted, element of Group 16 substituted or halogen, or two or more R 'can be joined to form a ring or ring system. In one embodiment, the metallocene type catalyst compounds with bridge of formula (II) have two or more bridge groups A (EP 664 301 B1).

In one embodiment, the catalyst compounds Metallocene type are those in which the R substituents on the bulky ligands L A and L B of the formulas (I) and (II) are substituted with the same or different number of substituents on each of the bulky ligands. In other embodiment, the bulky ligands L A and L B of the formulas (I) and (II) are different from each other.

Other catalyst compounds and metallocene-type catalyst systems useful in the invention may include those described in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296. 434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363, 5,856,547,
5,858,903, 5,859,158, 5,900,517, 5,939,503 and 5,962,718 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221, and European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1 -0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 739 361, EP-B1-0 748 821 and EP-B1-0 757 996, all of which are incorporated completely here for reference.

In one embodiment, the catalyst compounds Metallocene type useful in the invention include compounds of mono-metallocene type with heteroatom bridge. These types of catalysts and catalyst systems are described in, for example, PCT publications WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637, and in U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and in European publication EP-A-0 420 436, all of which are fully incorporated here by reference.

In this embodiment, the catalyst compound of Metallocene type is represented by the formula:

(III) L C AJMQ_ {n}

in which M is a metal atom from Group 3 to 16 or a metal selected from the Actinide Group and lanthanides from the Periodic Table of the Elements, preferably M is a transition metal from Group 4 to 12, and more preferably M is a transition metal of Group 4, 5 or 6 and, most preferably, M is a transition metal of Group 4 in any oxidation state, especially titanium; L C is a bulky substituted or unsubstituted ligand bound to M; J is attached to M; A is attached to M and J; J is an auxiliary ligand of heteroatom; and A is a bridge group; Q is an anionic ligand univalent; and n is the integer 0, 1 or 2. In the formula (III) above, L C, A and J form a system of fused rings. In one embodiment, L C of the formula (III) is as defined above for L A, A, M and Q of the formula (III) are as defined above in the formula (I).

In formula (III), J is a ligand that contains heteroatom in which J is an element with a number of coordination of three of Group 15 or an element with a number of coordination of two of Group 16 of the Periodic Table of the Elements. Preferably, J contains a nitrogen atom, phosphorus, oxygen or sulfur, the most preferred being nitrogen.

In another embodiment, the catalyst compound of metallocene type is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a ligand with substituted or unsubstituted pi bond, and one or more heteroalyl moieties, such as those described in the patents of United States numbers 5,527,752 and 5,747,406 and publication EP-B1-0 735 057, all of which are fully incorporated here by reference.

In one embodiment, the catalyst compound of metallocene type is represented by the formula

(IV) L D MQ 2 (YZ) X_ {n}

where M is a Group 3 metal a 16, preferably a transition metal from Group 4 to 12, and what more preferably a transition metal of Group 4, 5 or 6; L D is a bulky ligand bound to M; each Q is attached independently to M; and Q_ {2} (YZ) forms a ligand polycarbonate unicarded; A or Q is a univalent anionic ligand also attached to M; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (IV), L and M are as defined above for formula (I). Q is as defined above.  for formula (I), preferably Q is selected from the group that it consists of -O-, -NR-, -CR2 -, and -S-; Y is either C or S; Z se select from the group consisting of -OR, -NR2, -CR_3, -SR, -SiR 3, -PR 2, -H and aryl groups substituted or not substituted, with the proviso that, when Q is -NR-, then Z is selected from one of the group consisting of -OR, -NR_ {2}, -SR, -SiR3, -PR_2 and -H; R is selected from a group that contains carbon, silicon, nitrogen, oxygen and / or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably a group alkyl, cycloalkyl or aryl; n is an integer from 1 to 4, preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is a carbamate, carboxylate or other residue heteroalyl described by the combination of Q, Y and Z.

In another embodiment of the invention, the metallocene type catalyst compounds are complex ligands heterocyclics where bulky ligands, the ring (s) or ring system (s) include one or more heteroatoms or one of their combinations. Examples no Heteroatom limitation includes an element of Group 13 to 16, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin. Examples of these catalyst compounds of Metallocene type are described in WO 96/33202 publications, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095 (complexes of dicarbamoyl metal) and in the document EP-A1-0 874 005 and the patents of United States numbers 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417 and 5,856,258, all of which are incorporated Here by reference.

In another embodiment, the catalyst compounds Metallocene type are the complexes known as catalysts transition metal based on bidentate ligands containing pyridine or quinoline moieties, such as those described in the U.S. application serial number 09 / 103,620, filed on 23 June 1998, which is incorporated here by reference. In other embodiment, the metallocene type catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, which are fully incorporated here by reference.

In one embodiment, the catalyst compound of Metallocene type is represented by the formula:

(V) ((Z) XA_ {t} (YJ)) q MQ_ {n}

where M is a selected metal from Group 13; Q is attached to M and each Q is a monovalent anion, divalent or trivalent; X and Y are attached to M; one or more of X and Y they are heteroatoms, preferably both X and Y are heteroatoms; Y it is contained in a heterocyclic ring J, where J comprises from 2 to 50 atoms other than hydrogen, preferably 2 to 30 carbon atoms; Z is attached to X, where Z comprises 1 to 50  atoms other than hydrogen, preferably 1 to 50 atoms carbon, preferably Z is a cyclic group containing 3 up to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridge group attached to at least one of X, Y or J, preferably X and J; q is 1 or 2; n is an integer from 1 to 4, depending on the oxidation state of M. In a embodiment, where X is oxygen or sulfur, then Z is optional. In another embodiment, where X is nitrogen or phosphorus, then Z It is present. In one embodiment, Z is preferably a group aryl, more preferably an aryl group replaced.

Other metallocene catalyst compounds

It is within the scope of this invention, in one embodiment that the metallocene type catalyst compounds include Ni 2+ and Pd 2+ complexes described in the articles by Johnson, et al ., "New Pd (II ) - and Ni (II) - Based Catalysts for Polymerization of Ethylene and a-Olefins ", J. Am. Chem. Soc., 1995, 117, 6414-6415, and Johnson, et al .," Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalysts ", J. Am. Chem. Soc., 1996, 118, 267-168 and publications WO 96/23010, published August 1, 1996 and WO 99/02472 and U.S. Patent Nos. 5,852,145, 5,866,663 and 5,880,241, all of which are incorporated herein by reference. These complexes can be either dialkyl ether adducts or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the activators of this invention described below.

Also included as metallocene catalysts are the diimine-based ligands of Group 8 to 10 metal compounds described in PCT publications WO 96/23010 and WO 97/48735 and in the work of Gibson, et al ., Chem. Comm., Pp. 849-850 (1998), all of which are incorporated herein by reference.

Other metallocene type catalysts are the metal imide complexes of Group 5 and 6 described in EP-A2-0 816 348 and US Patent No. 5,851,945, which is incorporated herein by reference. In addition, metallocene type catalysts include Group 4 compounds of bis (arylamido) bridged described by DH McConville, et al ., In Organometallics 1195, 14, 5478-5480, which is incorporated herein by reference. In addition, bis (amido) bridged catalyst compounds are described in WO 96/27439, which is incorporated herein by reference. Other metallocene type catalysts are described as bis (hydroxyaromatic nitrogen ligands) in US Patent No. 5,852,146, which is incorporated herein by reference. Other metallocene type catalysts containing one or more Group 15 atoms include those described in WO 98/46651, which is incorporated herein by reference. Still other metallocene type catalysts include those multinuclear metallocene type catalysts such as those described in WO 99/20665, which is incorporated herein by reference.

It is also contemplated that, in one embodiment, the metallocene type catalysts of the invention described previously include your structural or optical isomers or enantiomerics (meso and racemic isomers, for example, see U.S. Patent No. 5,852,143, incorporated herein by reference) and their mixtures.

Activator and activation methods for compounds metallocene type catalysts

The metallocene type catalyst compounds bulky ligand described above are typically activated  in various ways to give catalyst compounds that have a vacant coordination site that will coordinate, insert and polymerize olefin (s).

For the purposes of this specification of patent and the appended claims, the term "activator"  defined to be any compound or component or method that can activate any of the type catalyst compounds metallocene of the invention as described above. The non-limiting activators, for example, may include an acid of Lewis or a non-coordinating ionic activator or ionizing activator or any other compound that includes Lewis bases, aluminum alkyls, type cocatalysts conventional and its combinations that can convert a compound neutral metallocene type catalyst in a metallocene cation catalytically active. It is within the scope of this invention use alumoxane or modified alumoxane as an activator, and / or use also ionizing, neutral or ionic activators, such as tetrakis (pentafluorophenyl) boron tri (n-butyl) ammonium, a precursor of trisperfluorophenylboro metalloid or a metalloid precursor of trisperfluoronaphthylboro, polyhalogenated heteroborane anions (WO 98/43983) or their combinations, which could ionize the compound neutral metallocene type catalyst.

In one embodiment, the activator is a compound which contains Group 13 metal that reacts with the acid itself carboxylic to form, for example, a carboxylate salt of metal.

In one embodiment, a activation method that uses ionizing ionic compounds that do not they contain an active proton but are capable of producing both a metallocene-type catalyst cation as a non-coordinating anion, and are described in the documents EP-A-0 426 637, EP-A-0 573 403 and the patent of United States No. 5,387,568, all of which are incorporated herein by reference.

There are several methods of preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924 .018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031,
5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346, and European publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594 218 and EP-B1-0 586 665, and PCT publication WO 94/10180, all of which are fully incorporated herein by reference.

Organoaluminum compounds as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminum and the Similar.

The ionizing compounds may contain a active proton or some other cation associated with but not coordinated with or only loosely coordinated with the remaining ion of the compound ionizing Such compounds and the like are described in the European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and the patents of United States numbers 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124, and the patent application for United States Serial No. 08/285,380, filed August 3, 1994, all of which are fully incorporated here by reference.

Other activators include those described in the PCT publication WO 98/07515, such as tri (2,2 ', 2' '- nonafluorobiphenyl) fluoroaluminate,  which publication is fully incorporated here by reference. Also contemplated by the invention are combinations of activators, for example, alumoxanes and ionizing activators in combinations, see, for example, the document EP-B1-0 573 120, publications of PCT WO 94/07928 and WO 95/14044 and United States patents Nos. 5,153,157 and 5,453,410, all of which are incorporated completely here for reference. Publication WO 98/09996, incorporated herein by reference, describes activating compounds metallocene type catalysts with perchlorates, periodate and iodates, including their hydrates. Publications WO 98/30602 and WO 98/30603, incorporated by reference, describe the use of (2,2'-bisphenyl-dithrimethylsilicate) .4THF lithium as activator for a catalyst compound of type metallocene WO 99/18135, incorporated here by reference, describes the use of activators of organo-boron-aluminum. The document EP-B1-0 781 299 describes the use of a silyllium salt in combination with a compatible anion and not coordinator Activation methods such as use radiation (see document EP-B1-0 615 981, incorporated here by reference), electrochemical oxidation and the like, such as activation methods for the purpose of converting the compound, or precursor, neutral metallocene catalyst in a cation of Metallocene type capable of polymerizing olefins. Other activators or methods for activating a metallocene catalyst compound are described, for example, in United States patents Nos. 5,849,852, 5,859,653 and 5,869,723 and WO publications 98/32775 and WO 99/42467 (bis (tris (pentafluorophenyl) borane) benzimidazolide of dioctadecylmethylammonium), which are incorporated here by reference.

It is also within the scope of this invention. than the metallocene catalyst compounds above described can be combined with one or more of the compounds catalysts represented by formulas (I) to (V) with one or more activators or activation methods described above.

It is further contemplated by the invention that others catalysts can be combined with catalyst compounds of the metallocene type of the invention. For example, see patents of the United States numbers 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811 and 5,719,241, all of which are incorporated completely here for reference. It is also contemplated that one any of the metallocene catalyst compounds of the invention have at least one labile group containing fluoride or fluorine, as described in US application No. of series 09 / 191.916, presented on November 3, 1998.

In another embodiment of the invention, one or more catalyst compounds or metallocene catalyst systems  can be used in combination with one or more compounds catalysts or catalyst systems of conventional type. Non-limiting examples of catalysts and catalyst systems mixed are described in United States patents numbers 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031, and the PCT publication WO 96/23010, published August 1, 1996, all of which are fully incorporated here by reference.

Carboxylic acids and salts of carboxylic acids

In one embodiment, the carboxylic acid used in The process of the invention is represented by the following formula:

RCOOH

where R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 up to 50 carbon atoms, or hydrogen.

Non-limiting examples of R in the previous formula include hydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl hydrocarbyl radicals, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated. In An embodiment of the invention, R is a hydrocarbyl radical that has greater than or equal to 8 carbon atoms, preferably greater than or equal to 12 carbon atoms, and more preferably greater than or equal to 17 carbon atoms. In another embodiment, R is a hydrocarbyl radical having from 17 to 90 atoms of carbon, preferably 17 to 72, and most preferably from 17 to 54 carbon atoms.

For the purposes of this specification of patent and of the appended claims, the expression "salt of metal carboxylate "is any salt of mono, di or tricarboxylic with a metal portion of the Periodic Table of The elements. Non-limiting examples include acid salts. aliphatic, aromatic, saturated or unsaturated carboxylic or saturated cyclics where the carboxylate ligand has preferably from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobutylacetate, t-butylacetate, caprylate, heptane, pelargonate, undecanoate, oleate, octoate, palmitate, Myristate, margarate, stearate, aracato and tercosanoate. Examples no Limitations of the metal portion include a metal from the Table Periodic of the Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.

In one embodiment, the carboxylic acid and the compound containing Group 13 metal of a product of reaction is represented by the following general formula:

M (Q) x (OOCR) y

where M is a Group 13 metal; Q it is halogen, hydrogen, a hydroxy or hydroxide group, alkyl, alkoxy, aryloxy, siloxy, silane sulfonate or siloxane; R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms; y x is a number integer from 0 to 3, e y is an integer from 1 to 4, and the sum of x and y is equal to the valence of the metal. In a preferred embodiment of the above formula and is an integer from 1 to 3, preferably 1 to 2.

Non-limiting examples of R in the formula Above include hydrocarbyl radicals that have 2 to 100 carbon atoms and include alkyl, aryl, aromatic radicals, aliphatic, cyclic, saturated or unsaturated. In an embodiment of the invention, R is a hydrocarbyl radical having greater than or equal to 8 carbon atoms, preferably greater than or equal to 12 carbon atoms and more preferably greater than or equal to 17 carbon atoms In another embodiment, R is a hydrocarbyl radical having from 17 to 90 carbon atoms, preferably 17 up to 72, and most preferably from 17 to 54 atoms of carbon.

Non-limiting examples of Q in the formula above include one or more, same or different, groups that they contain hydrocarbon such as alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, alkylamine, arylamine, alkyl phosphide and alkoxy having from 1 Up to 30 carbon atoms. The hydrocarbon containing group It can be linear, branched or even substituted. Also, Q, in one embodiment, in an inorganic group such as a halide, sulfate or phosphate.

In one embodiment, the carboxylate salts of Most preferred metal are aluminum carboxylates such as mono, di and aluminum triestearates, octoates, oleates and aluminum cyclohexylbutyrates. Still in another embodiment preferred, the metal carboxylate salt is (CH 3 (CH 2) 16 COO) 3 Al, a aluminum triestearate (preferred melting point 115 ° C), (CH 3 (CH 2) 16 COO) 2 Al-OH,  an aluminum distearate (preferred melting point 145 ° C), and a CH 3 (CH 2) 16 COO-Al (OH) 2,  an aluminum monostearate (preferred melting point 155 ° C).

Commercially available metal carboxylate salts non-limiting available, for example, include stearate Witco Aluminum No. 18, Witco Aluminum Stearate No. 22, Stearate aluminum Witco nº 132 and aluminum stearate Witco EA power quality, all of which are available from Witco Corporation, Memphis, Tennessee.

In one embodiment, the carboxylate salt of metal has a melting point from around 30 ° C to around 250 ° C, more preferably from around 37 ° C up to about 220 ° C, even more preferably from around 50 ° C to about 200 ° C, and most preferably from about 100 ° C to about 200 ° C. In the most preferred embodiment the metal carboxylate salt is a aluminum stearate that has a melting point in the range from about 135 ° C to about 165 ° C.

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In another preferred embodiment, the salt of metal carboxylate has a melting point greater than the polymerization temperature in the reactor.

Other examples of metal carboxylate salts include titanium stearate, tin stearates, stearates calcium, zinc stearates, boron stearate, and stearates strontium.

General supports, vehicles and support techniques

The catalyst compounds and systems metallocene type catalysts described above can be combine with one or more support materials or vehicles using one of the support methods well known in the art or as describe later. For example, in the most preferred embodiment, the catalyst compound or metallocene catalyst system it is supported, for example, deposited on, in contact with, vaporized with, attached to or incorporated into, adsorbed or absorbed in or on a support or vehicle.

The terms "support" or "vehicle" are use interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials. Examples no Limitations of inorganic support materials include oxides inorganic and inorganic chlorides. Other vehicles include resinous support materials such as polystyrene, supports functionalized or crosslinked organics, such as poly (styrene-civilibbenzene), polyolefins or compounds polymeric, or any other organic support material or inorganic and the like, or mixtures thereof.

Appropriate vehicles with inorganic oxides which include the metal oxides of Group 2, 3, 4, 5, 13 or 14. The Preferred supports include silica, alumina, silica-alumina and mixtures thereof. Other useful supports include magnesia, titania, zirconia, magnesium chloride, Montmorillonite (EP-B1-0 511 665), Philosilicate, zeolites, talc, clays and the like. I also know you can use combinations of these support materials, for example, silica-chrome, silica-alumina, silica-titania and the Similar. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 B1, which is incorporated herein by reference. Other materials Support materials include nanocomposite materials as described in the  PCT publication WO 99/47598, which is incorporated here by reference.

It is preferred that the vehicle, the most preferably an inorganic oxide, has a specific surface in the range from about 10 to about 700 m2 / g, pore volume in the range from about 0.1 up to about 4.0 cm3 / g and an average particle size in the range from about 5 to about 500 µm. More preferably, the specific surface of the vehicle is in the range from about 50 to about 500 m2 / g, the pore volume from about 0.5 to about 3.5 cm3 / g and the average particle size from around 10 to about 200 µm. The most preferably, the specific surface of the vehicle is in the range from about 100 to about 1000 m2 / g, pore volume from about 0.8 to about 5.0 cm3 / g and the average particle size is from about 5 up to about 100 µm. The average pore size of the vehicle  of the invention has a pore size in the range from 10 up to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 450 \ ring {A}.

Examples to support the metallocene type catalyst systems of the invention are described in U.S. Patent Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892, 5,240 .894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032,
5,770,664, 5,846,895 and 5,939,348 and U.S. applications serial numbers 271,598, filed July 7, 1994 and 788,736 filed January 23, 1997, and PCT publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494, all of which are fully incorporated herein by reference.

In one embodiment, the weight percentage of the carboxylic acid to the weight of the total supported catalyst system (the catalyst compound, preferably a catalyst compound metallocene type, activator, vehicle and salt of metal carboxylate) is in the range from about 0.1 percent by weight up to about 50 percent by weight, preferably in the range from 0.5 weight percent to about 25 percent by weight, more preferably in the range from about 1 percent by weight to around 10 percent by weight, and most preferably in the range from about 2 percent by weight to about 5 percent weight percent

In another embodiment, the acid level carboxylic in the reactor bed is in the range from around 1 ppm (part per million) up to about 2 per weight percent, preferably in the range from about 3 ppm up to about 1 percent by weight, more preferably in the range from about 5 ppm to about 500 ppm, and most preferably in the range from about 5 ppm up to about 50 ppm.

There are several other methods in the art for withstand a catalyst compound or catalyst system of polymerization of the invention. For example, the compound metallocene type catalyst of the invention may contain a polymer bound ligand as described in United States patents United numbers 5,473,202 and 5,770,755, which are incorporated completely here by reference; the type catalyst system Metallocene of the invention can be spray dried as described in U.S. Patent No. 5,648,310, which is fully incorporated here by reference; the support used with the metallocene type catalyst system of the invention is functionalizes as described in the European publication EP-A-0 802 203, which is incorporated completely here by reference, or at least one substituent or labile group as described in the patents of United States number 5,688,880, which is fully incorporated here by reference

In a preferred embodiment, the invention creates a supported metallocene type catalyst system that includes a surface modifier used in system preparation supported catalyst as described in PCT WO publication 96/11960, which is fully incorporated here by reference. The catalyst systems of the invention can be prepared in presence of an olefin, for example, 1-hexene.

A preferred method to produce a system supported metallocene type catalyst is described below and It is described in the US applications serial numbers 265,533, filed on June 24, 1994, and 265,532, filed on June 24, 1994, and PCT publications WO 96/00245 and WO 96/00243, both published on January 4, 1996, all of which They are fully incorporated here by reference. In this method preferred, the metallocene catalyst compound is suspended in a liquid to form a metallocene solution and a separate solution containing an activator and a liquid. The liquid  it can be any compatible solvent or other liquid capable of form a solution or the like with the catalyst compounds of metallocene type and / or the activator of the invention. In the realization more preferred, the liquid is a cyclic, aliphatic or hydrocarbon aromatic, most preferably toluene. The solutions of metallocene type catalyst compound and activator are mixed together, they are heated and added to a porous support, optionally a heated porous support, or a porous support is added, optionally a porous support heated to the solutions, of so that the total volume of the catalyst compound solution metallocene type and activator solution or solution of metallocene type catalyst compound and the activator is smaller than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than twice, the preferred ranges from 1.1 times up to 3.5 times and most preferably in the range from 1.2 to 3 times.

Procedures for measuring the total pore volume of a porous support are well known in the art. Details of one of these procedures are discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (specifically see pages 67-96). This preferred procedure involves the use of a conventional BET apparatus for nitrogen absorption. Another method well known in the art is described in the work of Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration , vol. 28, No. 3, Analytical Chemistry 332-334 (March 1956).

The mole ratio of the component metal metal activator of catalyst type compounds Supported metallocene is in the range between 0.3: 1 to 1000: 1, preferably 20: 1 to 800: 1, and most preferably 50: 1 to 500: 1. When the activator is an ionizing activator, such like those based on anion tetrakis (pentafluorophenyl) boron, the mole ratio from the metal of the activating component to the metal component of the metallocene type catalyst is preferably in the range between 0.3: 1 to 3: 1.

In an embodiment of the invention, prepolymerize olefin (s), preferably olefin (s) or alpha-olefin (s) of C 2 to C 30, preferably ethylene or propylene or its combinations, in the presence of the metallocene catalyst supported of the invention before the main polymerization. The prepolymerization can be carried out by loads or in continuous in the gas phase, in solution or in suspension, including at high temperatures Prepolymerization can take place with any monomer or combination of olefin and / or in the presence of any molecular weight control agent, such as hydrogen. For examples of prepolymerization procedures see patents United States numbers 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and the European publication EP-B-0 279 863 and the publication of the PCT WO 97/44371, all of which are fully incorporated here by reference

The supported catalysts of the invention described above are suitable for use in procedures of prepolymerization and / or polymerization over a wide range of temperatures and pressures Temperatures can be in the range from -60 ° C to about 280 ° C, preferably from 50ºC to around 200ºC, and the pressures used they can be in the range from 0.1013 MPa to around 50.65 MPa or greater.

In one embodiment, the procedure of this invention is directed towards the polymerization of olefin (s) in a polymerization reactor in the presence of a compound metallocene catalyst comprising a Group 4 metal, a inorganic oxide support, a carboxylic acid and a compound that contains Group 13 metal and, optionally, an activator; at that the catalyst compound is supported on an oxide inorganic to form a metallocene catalyst system supported, and in which the metallocene catalyst system supported is added to the reactor separately from the compound that It contains Group 13 metal and carboxylic acid; and in which the mole ratio of carboxylic acid to compound containing Group 13 metal is from 0.5 to less than 2.0.

In a further embodiment of the procedure described above, the Group 13 metal compound is added to the reactor before the addition of the olefin (s).

In one embodiment, the procedure of this invention is directed towards the polymerization of olefin (s) in a reactor in the presence of a catalyst system, the catalyst system a metallocene catalyst compound that it comprises a Group 4 metal, a support and an activator, the procedure comprising the steps of:

(to)

        introduce a compound containing Group 13 metal into the reactor; followed by

(b)

        introducing a carboxylic acid and the catalyst system into the reactor, the carboxylic acid added separately from the system catalyst; and in which the molar ratio of carboxylic acid to Group 13 metal containing compound is from 0.5 to lower that 2.0.

In a further embodiment of the procedure described above, the Group 13 metal compound is added to the reactor before the addition of the olefin (s).

In one embodiment, the procedure of this invention is directed towards the polymerization of one or more olefin (s) in a reactor in the presence of a compound metallocene catalyst comprising a Group 4 metal, a inorganic oxide support and a metal-containing compound of the Group 1 and, optionally, an activator, in which the acid carboxylic is added to the reactor in an amount sufficient to substantially maintain the catalyst activity of polymerization; in which the catalyst compound is supported over inorganic oxide to form a catalyst system of supported metallocene, and in which the catalyst system of Supported metallocene is added to the reactor separately from the compound containing the Group 13 metal and carboxylic acid; and in the that the mole ratio of carboxylic acid to compound that contains the metal of Group 13 is from 0.5 to less than 2.0.

In a further embodiment of the procedure described above, the Group 13 metal compound is added to the reactor before the addition of the olefin (s).

The polymerization process includes a solution procedure, gas phase, suspension phase and each other high pressure, or one of its combinations. Is particularly preferred a gas phase or phase polymerization in suspension of one or more olefins, at least one of which is ethylene or propylene.

In one embodiment, the procedure of this invention is directed towards a polymerization process in solution phase, high pressure, suspension or gas of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly very suitable for the polymerization of two or more olefin monomers of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-dean.

Other monomers useful in the process of invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated dienes or not conjugates, polyenes, vinyl monomers and cyclic olefins. The non-limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylideneborbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention an ethylene copolymer is produced, where with ethylene is copolymerized in a gas phase process a comonomer that has at least one alpha-olefin that have from 4 to 15 carbon atoms, preferably from 4 up to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms

In another embodiment of the procedure of the invention, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerization process, particularly a process in gas phase or suspended phase, to polymerize propylene alone or with one or more different monomers including ethylene and / or other olefins having from 4 to 12 carbon atoms. Be they can produce polypropylene polymers using the catalysts of metallocene type particularly bridged as described in U.S. Patents Nos. 5,296,434 and 5,278,264, both which are incorporated here by reference.

Typically, in a procedure of gas phase polymerization a continuous cycle is used where, in a part of the cycle of a reactor system, a gas stream cyclic, otherwise known as recycle stream or medium of fluidization, it is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle through an external cooling system  to the reactor Generally, in a fluidized bed procedure by gas to produce polymers, it is continuously cycled through from the fluidized bed a gaseous stream containing one or more monomers in the presence of a catalyst under conditions reactive The gas stream is extracted from the fluidized bed and is recycle back to the reactor. Simultaneously, the product polymer is extracted from the reactor and new monomer is added to replace the polymerized monomer. (See, for example, the U.S. Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, all of which are fully incorporated here by reference).

The reactor pressure in a procedure in gas phase can vary from around 690 kPa to around  3448 kPa, preferably in the range from about 1379 kPa to about 2759 kPa, more preferably in the range from about 1724 kPa to about 2414 kPa.

The reactor temperature in the process in gas phase can vary from around 30 ° C to around 120 ° C, preferably from about 60 ° C to about 115 ° C, more preferably in the range from about 70 ° C up to 110 ° C, and most preferably in the range from around 70ºC to around 95ºC.

Other gas phase procedures contemplated by the process of the invention include methods of serial or multistage polymerization. Also the procedures in gas phase contemplated by the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375 and European publications EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202 and EP-B-0 634 421, all of which fully incorporated here by reference.

In a preferred embodiment, the reactor used in the present invention is capable of and the procedure of the invention is to produce greater than 227 kilograms of polymer per hour (kg / h) up to about 90,900 kg / h or greater of polymer, preferably greater than 455 kg / h, more preferably greater than 4540 kg / h, even more preferably greater than 11,300 kg / h, still more preferably greater than 15,900 kg / h, even more preferably greater than 22,700 kg / h and most preferably greater than 29,000 kg / h up to 45,500 kg / h.

A suspension polymerization process generally uses pressures in the range from around 0.1013 to around 5,065 MPa and even higher and temperatures in the range of 0 ° C to about 120 ° C. In a suspension polymerization, a polymer suspension is formed in solid particles in a liquid polymerization diluent medium to which are added ethylene and the comonomers and, often, hydrogen, together with the catalyst. The suspension that includes diluent is intermittently or continuously withdraws from the reactor where Volatile components are separated from the polymer and recycled, optionally after distillation, to the reactor. Thinner liquid used in the polymerization medium is typically a alkane having from 3 to 7 carbon atoms, preferably a branched alkane The medium used should be low liquid polymerization conditions and relatively inert. When use a propane medium, the procedure must be operated above of the critical temperature and pressure of the reaction diluent. Preferably, a hexane medium or one of isobutane

A preferred polymerization technique of the invention is referred to as a particulate polymerization,  or a suspended procedure where the temperature is maintained below the temperature at which the polymer enters solution. Such a technique is well known in the art and is described, for example, in U.S. Patent No. 3,248,179, which is fully incorporated here by reference. Other procedures in suspension include those that employ a loop reactor and those that use a plurality of agitated reactors in series, Parallel or their combinations. Non-limiting examples of Suspended procedures include continuous procedures of Loop type or stirred tank. Also, other examples of Suspended procedures are described in the patent of United States No. 4,613,484, which is fully incorporated here by reference

In one embodiment, the reactor used in the procedure of the invention is capable of and the procedure of the invention is to produce greater than 907 kilograms of polymer per hour (kg / h), more preferably greater than 2268 kg / h, and most preferably greater than 4540 kg / h. In another embodiment, the reactor in suspension used in the process of the invention is producing greater than 6804 kg / h, preferably greater than 11,340 kg / h up to about 45,500 kg / h.

Examples of solution procedures are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555 and in PCT WO publication 99/32525, which are fully incorporated here by reference.

A preferred method of the invention is in which the procedure, preferably a phase procedure in suspension or gas, it is operated in the presence of a system metallocene catalyst of the invention and in the absence of, or essentially free of any debugger, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexyl aluminum chloride diethyl aluminum, dibutyl zinc and the like. This Preferred procedure is described in PCT WO publication 96/08520 and in U.S. Patents Nos. 5,712,352 and 5,763,543, which are fully incorporated herein by reference.

Polymeric products

The polymers produced by the process of The invention can be used in a wide variety of products and end use applications. The polymers produced by the Process of the invention include linear low polyethylene density, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.

Polymers, typically polymers based on ethylene, have a density in the range from 0.86 g / cm3 up to 0.97 g / cm3, preferably in the range from 0.88 g / cm3 to 0.965 g / cm3, more preferably in the range from 0.900 g / cm3 to 0.96 g / cm3, even more preferably in the range from 0.905 g / cm3 to 0.95 g / cm3, even more preferably in the range from 0.910 g / cm3 to 0.940 g / cm3, and most preferably greater than 0.915 g / cm3, preferably greater than 0.920 g / cm3, and most preferably greater than 0.925 g / cm3. The Density is measured in accordance with ASTM D-1238.

The polymers produced by the process of the invention typically have a weight distribution molecular, an average molecular weight weighted to molecular weight numerical average (M_ {w} / M_ {n}) greater than 1.5 to around from 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than around 8, and most preferably from 2.5 to 8.

Also, the polymers of the invention have typically a narrow distribution of the composition, measured by the Composition Distribution Width Index (CDBI, in its acronym in English). Additional details of the determination of CDBI of a copolymer are known to those skilled in the art. See, for example, PCT patent application WO 93/03093, published on February 18, 1993, which is fully incorporated Here by reference.

Polymers catalyzed with type catalyst metallocene of the invention in one embodiment have CDBIs generally in the range of greater than 50% to 100%, preferably 99%, preferably in the range of 55% to 85%, and more preferably 60% up to 80%, even more preferably greater than 60%, still even more preferably greater than 65%.

In another embodiment, the polymers produced using the metallocene catalyst system of the invention they have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%.

The polymers of the present invention, in a embodiment, have a melt index (MI) or (I2), measured by ASTM D-1238-E, in the interval from 0.01 dg / min to 1000 dg / min, more preferably from around 0.01 dg / min up to about 100 dg / min, even more preferably from about 0.1 dg / min to about 50 dg / min, and most preferably from about 0.1 dg / min to around 10 dg / min

The polymers of the invention, in a realization, they have a melt index ratio (I_ {21} / I_ {2}) (I_ {21} is measured by ASTM-D-1238-F) from 10 to less than 25, more preferably from about 15 up to less than 25.

The polymers of the invention, in one embodiment preferred, have a melt index ratio (I_ {21} / I_ {2}) (I_ {21} is measured by ASTM-D-1238-F) from preferably greater than 25, more preferably greater than 30, even more preferably greater than 40, even more preferably greater than 50 and most preferably greater than 65. In one embodiment, the polymer of the invention may have a narrow molecular weight distribution and wide distribution of the composition, or vice versa, and may be the polymers described in U.S. Patent No. 5,798,427, incorporated herein by reference.

In yet another embodiment, polymers are produced based on propylene in the process of the invention. These polymers include atactic polypropylene, isotactic polypropylene, Hemiisotactic and syndiotactic polypropylene. Other polymers of Propylene include copolymers of propylene or impact blocks. Propylene polymers of these types are well known in the technique, see, for example, United States patents numbers  4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117, all which are incorporated here by reference.

The polymers of the invention can be mixed and / or co-extrude with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes produced by means of Ziegler-Natta catalysis conventional and / or bulky ligand metallocene type, elastomers, plastomers, low density and high polyethylene pressure, high density polyethylenes, polypropylenes and Similar.

The polymers produced by the The process of the invention and mixtures thereof are useful in forming operations such as extrusion and coextrusion of films, sheets and fibers, as well as blow molding, molding injection and rotational molding. The movies include movies blown or cast formed by coextrusion or by lamination useful such as shrink films, binding films, stretched films, sealing films, oriented films, packaging snacks, heavy duty bags, grocery bags, Baked and frozen food packaging, medical packaging, industrial coatings, membranes, etc., in applications in food contact or no food contact. Fibers include cast spinning, solution spinning and operations of melt-blown fiber for use in woven or non-woven form woven to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded items include tubing medical, coatings for wires and cables, pipes, geomembranes and coatings for ponds. The articles molded include single or multiple layer construction in shape of bottles, tanks, large hollow items, containers for rigid food and toys, etc.

Examples

In order to provide a better understanding of the present invention, including its representative advantages, The following examples are offered.

Density is measured according to ASTM-D-1238.

I_ {2} is measured by ASTM-D-1238-E.

I_ {21} is measured by ASTM-D-1238-F.

The fouling index in the tables Following illustrates the operability of the catalyst. The older Whatever the value, the greater the fouling observed. An index of Zero fouling means substantially without fouling or not visible. An fouling index of 1 is indicative of light fouling, where a light coating occurs partial polymer on the agitator blades of a reactor polymerization of isobutane in suspension of 2 liters and / or not reactor body coating. An fouling index of 2 is indicative of a fouling rather than light, where agitator blades have a polymer coating more heavy, similar to if they were painted, and / or the body wall of the reactor has some coating in a band of 2.54 to 5.08 cm wide in the wall of the rector. An fouling index of 3 It is considered medium fouling, where the agitator blade has a thicker, latex-like polymer coating on the agitator vane, some soft pieces in the reactor and / or something covering the reactor body with a band of 5.08 up to 7.62 cm wide over the reactor wall. An index of Fouling of 4 is evidence of fouling greater than average, where the agitator has a thick, latex-like coating, some harder pieces / balls of polymer and / or the band of Wall covering of the reactor body is from 7.62 up to 10.2 cm wide.

The Activity in the following tables is measured in grams of polyethylene (PE) per gram of catalyst polymerization-hour (gPE / gCat-h).

Example 1 Catalyst A Preparation

The metallocene type catalyst compound of bulky, bridged ligand, used in this example 1 is a dichloride dimethylsilyl bis (tetrahydroindenyl) zirconium (Me 2 Si (H 4 Ind) 2 ZrCl 2) available from Albemarle Corporation, Baton Rouge, Louisiana. The compound catalyst of (Me 2 Si (H 4 Ind) 2 ZrCl 2) was supported on dehydrated Crosfield ES-70 quality silica at 600 ° C, which had approximately 1.0 weight percent of Ignition loss (PEI) of water. PEI is measured by determining the weight loss of the support material that has been heated and maintained at a temperature of around 1000 ° C for around of 22 hours. Crosfield ES-70 quality silica It has an average particle size of 40 micrometers and is available from Crosfield Limited, Warrington, England.

The first stage in the manufacture of supported voluminous ligand metallocene type catalyst Above involves forming a precursor solution. 209 kg are added from bubbled and dried toluene to a stirred reactor after which add 482 kg of a 30 percent methylaluminoxane (MAO) by weight in toluene (available from Albemarle, Baton Rouge, Louisiana). 430 kg of a 2 solution is introduced into the reactor weight percent in toluene of the dichloride catalyst compound from dimethylsilyl bis (tetrahydroindenyl) zirconium and an additional 272 kg of toluene. The precursor solution is stirred then at 26.7 ° C to 37.8 ° C for one hour.

While stirring the previous solution of precursor, slowly added to the precursor solution 386 kg of Crosfield silica support dehydrated at 600 ° C and the mixture is stir for 30 min at 26.7 ° C to 37.8 ° C. At the end of the 30 minutes of stirring the mixture, 109 kg of a solution are added 10 percent by weight in toluene of AS-990 (N, N-bis (2-hydroxyethyl) octadecylamine) (C 18 H 37 N (CH 2 CH 2 OH) 2), available as Kemamine AS-990 from Witco Corporation, Memphis, Tennessee, along with a 50 kg rinse additional toluene and then the reactor contents are mixed for 30 min while heating to 79 ° C. After 30 min, vacuum is applied and the polymerization catalyst mixture is dried at 79 ° C for about 15 hours until it is a fluid powder. The final weight of the polymerization catalyst was 544 kg and it had a weight% of Zr of 0.35 and a weight% of Al of 12.0.

Comparative Example 1 and Examples 2 to 6

Polymerization procedure using catalyst A

A 2-liter autoclave reactor was loaded under a nitrogen purge, with 0.16 mmol of triethylaluminum (TEAL), followed by 20 cm3 of 1-hexene comonomer and 800 cm3 of isobutane diluent. The reactor contents are heated to 80 ° C after which 100 were polymerized separately mg of the supported polymerization catalyst, catalyst A, as continue: In each polymerization example, the polymerization catalyst concurrently with ethylene in the reactor to make a total reactor pressure of 2240 kPa. The reactor temperature was maintained at 85 ° C and the polymerization for 40 minutes. After 40 minutes, it cooled the reactor, ethylene was vented and the polymer was dried and weighed to Get the polymer performance. The following table 1 provides performance activity data as well as fouling characteristics observed using catalyst A without carboxylic acid, specifically stearic acid, and Examples 2 to 6 in which various amounts of acid were used stearic indicated in table 1.

TABLE 1

Example Stearic Acid: Quantity (cm3) Activity Index of fouling1 TEAL (moles) (gPE / gCat.h) Ex.C.1 None 0 1770 1.0 2 0.5 0.5 1575 1.0 3 0.5 1.0 1500 0.5 4 0.5 1.0 1455 0.5 5 1.0 1.0 1500 0.0 6 2.0 1.0 1365 2.0 ^ {1} \ begin {minipage} [t] {155mm} The scale for the Index of Dirting is from 0 to 2, where 0 is without fouling and 2 It is the worst fouling. \ end {minipage}

From table 1 above you can see in particular that, from greater than 0.5 moles of carboxylic acid to less than 2.0 moles, operability, indicated by the Pollution Index, improves greatly.

Examples 7 to 12

Polymerizations with various compounds containing metal from Group 13

In the following examples 7 to 12 were prepared separately stearic / alkyl metal solutions in vials at the molar ratio specified in table 2. Before adding the comonomer to the reactor, the amount was added to the reactor specified in table 2 of the prepared solutions. He polymerization procedure was carried out in the same way earlier than with comparative example 1 and examples 2 through 6. In Table 2, AE is stearic acid, TEAL is triethylaluminum, TIBAL is tri-isobutylaluminum, TNHAL is tri-n-octylaluminum and MAO is methylalumoxane.

TABLE 2

Example Solution performance (g) Activity Index of fouling3 (gPE / gCat.h) 7 TEAL 110 1650 1.0 8 AE / TEAL1 93 1395 0 9 AE / TIBAL1 86 1290 0 10 AE / TNHAL1 86 1290 0 eleven AE / MAO1 79 1185 0 12 TEAL2 92 1380 1.0 ^ {1} \ begin {minipage} [t] {155mm} It was added to the reactor before polymerization 1 cm3 of solution in hexane of molar ratio 1 to 1 of carboxylic acid to alkylaluminum. \ end {minipage} 2 The solution of TEAL in hexane was stirred as the other solutions without stearic acid (AE). 3 The fouling index of 0 means without fouling and 1 means that it it got dirty.

Although the present invention has been described in illustrated with reference to particular embodiments, the normally those skilled in the art will appreciate that the invention leads by itself to variations not necessarily illustrated here. For example, it is contemplated that two or more may be used supported catalyst compositions of the invention. For this reason, then, reference should be made only to attached claims for the purpose of determining the true Scope of the present invention.

Claims (17)

1. A procedure to polymerize olefin (s) in a polymerization reactor in the presence of metallocene catalyst compound comprising a metal of Group 4, an inorganic oxide support, a carboxylic acid and a Group 13 metal containing compound; in which the compound catalyst is supported on an inorganic oxide to form a supported metallocene catalyst system and in which the system supported metallocene catalyst is added to the reactor separately from the metal containing compound of Group 13 and the carboxylic acid; and in which the mole ratio of acid carboxylic to compound containing Group 13 metal is from 0.5 to less than 2.0. 2. The method of claim 1, in which carboxylic acid is represented by the formula RCOOH in which R is hydrocarbyl radical from 2 to 100 carbon atoms or hydrogen. 3. The method of claim 1, in which the compound containing Group 13 metal is a compound of organoaluminum or organoxyaluminum compound. 4. The method of claim 1, in which the carboxylic acid and the metal-containing compound of the Group 13 of a reaction product represented by the formula: M (Q) x (OOCR) y in which M is a Group metal 13; Q is a halogen, a hydroxide, alkoxy, aryloxy, siloxy group, silane or sulfonate; x is an integer from 0 to 3; and it is a integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M; and R is a hydrocarbyl radical that has from 4 to 24 atoms of carbon. 5. The composition of claim 4, in the that y is either 1 or 2, M is aluminum and Q is a hydroxyl group. 6. The method of claim 1, in that the procedure is a gas phase procedure and the carboxylic acid is a stearic acid. 7. The method of claim 1, in the one that the olefin (s) has from 2 to 20 carbon atoms 8. A procedure to polymerize olefin (s) in a reactor in the presence of a system catalyst, the catalyst system comprising a compound metallocene catalyst comprising a Group 4 metal, a support and an activator, the procedure comprising the steps from:

(to)

        introduce a compound containing Group 13 metal into the reactor; followed by

(b)

        introducing a carboxylic acid and the catalyst system into the reactor, the carboxylic acid added separately from the system catalyst; and in which the molar ratio of carboxylic acid to Group 13 metal containing compound is from 0.5 to lower that 2.0.

9. The method of claim 8, in which the activator is a compound that contains Group metal 13. 10. The method of claim 8, in which carboxylic acid is introduced continuously or intermittently. 11. The method of claim 8, in which carboxylic acid is represented by the formula RCOOH in which R is hydrocarbyl radical from 2 to 100 carbon atoms or hydrogen. 12. A procedure to polymerize one or more olefin (s) in a reactor in the presence of a compound metallocene catalyst comprising a Group 4 metal, a inorganic oxide support and a metal-containing compound of the Group 1, in which a carboxylic acid is added to the reactor in a sufficient amount to substantially maintain the activity of the polymerization catalyst; in which the catalyst compound is supported on inorganic oxide to form a system supported metallocene catalyst, and in which the system supported metallocene catalyst is added to the reactor separately from the metal containing compound of Group 13 and the carboxylic acid; and in which the molar ratio of acid carboxylic to compound containing Group 13 metal is from 0.5 to less than 2.0. 13. The method of claim 12, in that the reactor is a gas phase reactor. 14. The method of claim 12, in which the compound containing Group 13 metal is a compound of organoaluminum or an organoxyaluminum compound or one of its mixtures 15. The method of claim 12, in which carboxylic acid is a stearic acid. 16. The procedure of any of the claims 1, 8 or 12 wherein the metal compound of the Group 13 is added to the reactor before the addition of the (s) olefin (s). 17. The procedure of any of the claims 1 or 12, wherein the catalyst system of Supported metallocene further comprises an activator.